Since the classic work Metal-Catalyzed Oxidations of Organic Compounds (edited by R A Sheldon and J K Kochi, 1991), no book has been devoted to advances in the field of biomimetic oxidations, which was created nearly 18 years ago. This expanding research field is covered in this volume. All the different aspects of the modeling of oxidations catalyzed by metalloenzymes are dealt with.This invaluable book will be useful to postgraduates as well as researchers in academia and industry, and will also benefit second year university students.

Metal-Catalyzed Oxidations of Organic Compounds: Mechanistic Principles and Synthetic focuses on the oxidative transformations of functional groups. This book explores oxidation as being extensively used in the laboratory synthesis of fine organic chemicals and in the manufacture of large-volume petrochemicals. Organized into two parts encompassing 13 chapters, this book starts with an overview of the mechanistic principles of oxidation–reduction in biochemical, organic, and inorganic systems. This text then proceeds with a discussion of the use of molecular oxygen, hydrogen peroxide, and alkyl hydroperoxides as primary oxidants. Other chapters explore stoichiometric oxidations with metal oxidants, which include permanganate and chromic acid. This book discusses as well the synthetic applications of catalytic oxidations as well as the technology of petrochemical oxidation. The final chapter deals with the autoxidations of sulfur, phosphorus, and nitrogen compounds. This book is intended for chemists involved in organic synthesis, catalysis, and organometallic chemistry, both in academic institutions and in industrial laboratories.

In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this situation. Growing families of synthetic iron complexes that resemble active sites of metalloenzymes produce metal-based intermediates (rather than hydroxyl radicals) in reactions with oxygen donors. These complexes are very promising for selective oxygen and peroxide activation. In order to understand the mechanisms of metal-based small molecule activation, kinetically competent metal-oxygen intermediates must be identified. One of the grand challenges identified by the Department of Energy workshop "Catalysis for Energy" is understanding mechanisms and dynamics of catalyzed reactions. The research summarized herein focuses on detailed characterization of the formation and reactivity of various iron-peroxo- and iron-oxo intermediates that are involved in catalysis. Rates of rapid reactions were studied at low temperatures by a specialized technique termed cryogenic stopped-flow spectrophotometry. These measurements identified reaction conditions which favor the formation of catalytically competent oxidants. Chemical structures of reactive complexes was determined, and new, efficient catalysts for hydrocarbon oxidation were synthesized. Importantly, these catalysts are selective, they promote oxidation of hydrocarbons at a specific site. The catalysts are also efficient and robust, hundreds of cycles of substrate oxidation occur within minutes at room temperature. Furthermore, they enable utilization of environmentally friendly oxidants, such as hydrogen peroxide, which produces water as the only byproduct. Mechanistic insights uncovered the role of various acid-containing additives in catalytic oxidations. Proton delivery to the active catalytic sites facilitated oxidations, similarly to the catalytic pathways in metal-containing enzymes. Under certain conditions, two metals in one complex can act in concert, modeling the reactivity of a bacterial enzyme which converts methane into methanol. In related studies, a family of nickel complexes that react with carbon ...

The catalytic epoxidation of olefins plays an important role in the industrial production of several commodity compounds, as well as in the synthesis of many intermediates, fine chemicals, and pharmaceuticals. The scale of production ranges from millions of tons per year to a few grams per year. The diversity of catalysts is large and encompasses all the known categories of catalyst type: homogeneous, heterogeneous, and biological. This book summarizes the current status in these fields concentrating on rates, kinetics, and reaction mechanisms, but also covers broad topics including modeling, computational simulation, process concepts, spectroscopy and new catalyst development. The similarities and distinctions between the different reaction systems are compared, and the latest advances are described. - Comprehensive listing of epoxide products - Broad comparison of turnover frequencies of homogeneous, hetergeneous, main-group, biomimetic and biological catalysts - Analysis of the general strengths and weaknesses of varied catalytic systems - Detailed description of the mechanisms of reaction for classical and emerging catalysts

At the very latest, with the award of the 2001 Nobel Prize for work on asymmetric oxidation, there has been a need for a comprehensive book on such methods. Edited by J.-E. Backvall, one of the world's leaders in the field, this book fills that gap by covering the topic, from classical to green chemistry methods. He has put together a plethora of well-established authors from all over the world who cover every important aspect in high-quality contributions -- whether aerobic oxidation or transition metal-catalyzed epoxidation of alkenes. By providing an overview of this huge topic, this book represents an unparalleled aid for any chemist working in the field. Chapters include: Recent Developments in the Osmium-Catalyzed Dihydroxylation of Olefins Transition Metal-Catalyzed Epoxidation of Alkenes Organocatalytic Oxidation - Ketone-Catalyzed Asymmetric Epoxidation of Olefins Modern Oxidation of Alcohols using environmentally Benign Oxidants Aerobic Oxidations and Related Reactions Catalyzed by N-Hydroxyphthalimide Ruthenium-Catalyzed Oxidation of Alkenes, Alcohols, Amines, Amides, b-Lactams, Phenols, and Hydrocarbons Selective Oxidations of Sulfides and Amines Liquid Phase Oxidation Reactions Catalyzed by Polyoxometalates Oxidation of Carbonyl Compounds Mn-catalysed Oxidation with Hydrogen Peroxide

Advances in Inorganic Chemistry presents timely and informative summaries of the current progress in a variety of subject areas within inorganic chemistry ranging from bio-inorganic to solid state studies. Thisacclaimed serial features reviews written by experts in the area and is an indispensable reference to advanced researchers. Each volume of Advances in Inorganic Chemistry contains an index, and each chapter is fully referenced. - Comprehensive reviews written by leading experts in the field - An indispensable reference to advanced researchers - Includes 7 contributions covering important advances in inorganic chemistry

The activation of dioxygen by metal ions has both synthetic potential and biological relevance. Dioxygen is the cleanest oxidant for use in emission-free technologies to minimize pollution of the environment. The book gives a survey of those catalyst systems based on metal complexes which have been discovered and studied in the last decade. They activate molecular oxygen and effect the oxidation of various organic compounds under mild conditions. Much of the recent progress is due to a search for biomimetic catalysts that would duplicate the action of metalloenzymes. Mechanistic aspects are emphasized throughout the book. An introductonary chapter reviews the chemistry of transition metal dioxygen complexes, which are usually the active intermediates in the catalytic reactions discussed. Separate chapters are devoted to oxidation of saturated, unsaturated and aromatic hydrocarbons, phenols, catechols, oxo-compounds, phosphorus, sulfur and nitrogen compounds.

Advances in Inorganic Chemistry Volume 58 focuses on homogeneous biomimetic oxidation catalysis. Contributions by leading experts in the field cover important advances in inorganic and bioinorganic chemistry. Contributions include diversity-based approaches to selective biomimetic oxidation catalysis; the selective conversion of hydrocarbons with H2O2 using biomimetic non-heme iron and manganese oxidation catalysis; DNA oxidation by copper and manganese complexes; influences of the ligand in copper-dioxygen complex-formation and substrate oxidations; biomimetic oxidations by dinuclear and trinuclear copper complexes. In the final contribution the authors focus on green oxidation of alcohols using biomimetic copper complexes and enzymes as catalysts. Volume 58 provides another welcomed addition to the widely acclaimed series, Advances in Inorganic Chemistry.* Includes new information on the important advances in inorganic and bioinorganic chemistry * Each chapter is fully referenced * Contains comprehensive reviews written by leading experts in the field